EP4026817A1 - Harzformulierungen für aus polymer stammenden keramikmaterialien - Google Patents

Harzformulierungen für aus polymer stammenden keramikmaterialien Download PDF

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Publication number
EP4026817A1
EP4026817A1 EP22152781.5A EP22152781A EP4026817A1 EP 4026817 A1 EP4026817 A1 EP 4026817A1 EP 22152781 A EP22152781 A EP 22152781A EP 4026817 A1 EP4026817 A1 EP 4026817A1
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EP
European Patent Office
Prior art keywords
ceramic structure
group
molecule
preceramic
combinations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22152781.5A
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English (en)
French (fr)
Inventor
Zak Eckel
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HRL Laboratories LLC
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HRL Laboratories LLC
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Publication date
Application filed by HRL Laboratories LLC filed Critical HRL Laboratories LLC
Publication of EP4026817A1 publication Critical patent/EP4026817A1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C04B2235/726—Sulfur content
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/14—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention generally relates to formulations suitable for making preceramic polymers, which can be converted into ceramic structures.
  • Ceramic structures are typically sintered as compacted porous materials, severely decreasing the overall strength of the material. Thus, there exists a need for creating large, fully dense ceramic materials which possess the high strength of the parent material and are therefore useful for engineering applications.
  • Formulations have been described for creating ceramic materials, which can be printed (additively manufactured) with various methods such as stereolithography techniques and laser sintering. These are typically sintered powders or formulations with solid material suspended, typically producing porous structures. These methods are described in Zocca et al., “Additive Manufacturing of Ceramics: Issues, Potentialities, and Opportunities", J. Am. Ceram. Soc., 98 [7] 1983-2001 (2015 ).
  • ceramics are difficult to process, particularly into complex shapes. Because they cannot be cast or machined easily, ceramics are typically consolidated from powders by sintering or deposited in thin films. Flaws, such as porosity and inhomogeneity introduced during processing, govern the strength because they initiate cracks, and-in contrast to metals-brittle ceramics have little ability to resist fracture. This processing challenge has limited the ability to take advantage of ceramics' impressive properties, including high-temperature capability, environmental resistance, and high strength. Recent advances in additive manufacturing have led to a multitude of different techniques, but all additive manufacturing techniques developed for ceramic materials are powder-based layer-by-layer processes.
  • Preceramic polymers are a class of polymers which allow, via a thermal treatment, a conversion of a polymer part to a ceramic material. Typically, these preceramic polymers contain silicon (Si) in the molecular backbone, with the resulting material containing Si.
  • Si silicon
  • a stereolithography technique provides a method to build a 3D polymer microstructure in a layer-by-layer process.
  • This process usually involves a platform (e.g., substrate) that is lowered into a photomonomer bath in discrete steps.
  • a laser is used to scan over the area of the photomonomer that is to be cured (i.e., polymerized) for that particular layer.
  • the platform is lowered by a specific amount, determined by the processing parameters and desired feature/surface resolution, and the process is repeated until the complete 3D structure is created.
  • a stereolithography technique is disclosed in U.S. Patent No. 4,575,330 issued March 11, 1986 to Hull et al.
  • Direct, free-form 3D printing of preceramic polymers which can be converted to fully dense ceramics, is sought. What are needed are low-cost structures that are lightweight, strong, and stiff, but stable in the presence of a high-temperature oxidizing environment.
  • the monomers and polymeric systems preferably maintain properties so that they can be printed using stereolithography into complex 3D shapes. Ideally, the polymeric systems may be directly converted to fully dense ceramics with properties that approach the theoretical maximum strength of the base materials.
  • the present invention addresses the aforementioned needs in the art, as will now be summarized and then further described in detail below.
  • preceramic resin formulation comprising:
  • the first molecule is present from about 3 wt% to about 97 wt% of the formulation, for example.
  • At least one of the double bonds (or triple bonds) is located at a terminal position of the first molecule.
  • the first molecule may include one or more functional groups selected from the group consisting of vinyl, ethynyl, vinyl ether, vinyl ester, vinyl amide, vinyl triazine, vinyl isocyanurate, acrylate, methacrylate, diene, triene, and functional analogs thereof. In some embodiments, the first molecule includes two or more of such functional groups.
  • the second molecule is included in the preceramic resin formulation, the second molecule is present from about 0.1 wt% to about 97 wt% of the formulation, for example.
  • the second molecule may include one or more functional groups selected from the group consisting of thiol, alkyl, ester, amine, hydroxyl, and functional analogs thereof.
  • the second molecule may be chemically contained within one or more functional groups selected from the group consisting of thiol, alkyl, ester, amine, hydroxyl, and functional analogs thereof.
  • the R may be, or include, an inorganic group containing an element selected from the group consisting of Si, B, Al, Ti, Zn, P, Ge, S, N, O, and combinations thereof. In some embodiments, at least 10% (such as at least 40%) of the R is inorganic. In certain embodiments, at least 10% (such as at least 40%) of the R is Si.
  • the photoinitiator may be present from about 0.001 wt% to about 10 wt% of the formulation, for example.
  • the photoinitiator and/or the thermal free-radical initiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, camphorquinone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, benzophenone, benzoyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, and combinations or derivatives thereof.
  • the formulation further includes a radiation-trigger free-radical initiator that is active at a wavelength substantially different from the photoinitiator.
  • the preceramic resin formulation includes a thermal free-radical initiator
  • the formulation further includes a radiation-trigger free-radical initiator that is active at a wavelength substantially different from the photoinitiator.
  • the free-radical inhibitor may be present from about 0.001 wt% to about 10 wt% of the formulation, for example.
  • the free-radical inhibitor may be selected from the group consisting of hydroquinone, methylhydroquinone, ethylhydroquinone, methoxyhydroquinone, ethoxyhydroquinone, monomethylether hydroquinone, propylhydroquinone, propoxyhydroquinone, tert-butylhydroquinone, n-butylhydroquinone, and combinations or derivatives thereof.
  • the 3D-printing resolution agent may be present from about 0.001 wt% to about 10 wt% of the formulation, for example.
  • the 3D-printing resolution agent may be selected from UV absorbers, fluorescent molecules, optical brighteners, or combinations thereof.
  • the 3D-printing resolution agent is selected from the group consisting of 2-(2-hydroxyphenyl)-benzotriazole, 2-hydroxyphenyl-benzophenones, 2-hydroxyphenyl-s-triazines, 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole), 2,2'-(1,2-ethenediyl)bis(4,1-phenylene)bisbenzoxazole, and combinations or derivatives thereof.
  • a ceramic structure produced by polymerization, 3D printing, and thermal treatment (e.g., pyrolysis or sintering) of a preceramic resin formulation comprising:
  • the ceramic structure contains from about 0.01 wt% to about 20 wt% sulfur, such as from about 0.1 wt% to about 10 wt% sulfur.
  • the ceramic structure may be characterized by at least 50% theoretical density, preferably at least 75% theoretical density, and more preferably at least 95% theoretical density.
  • the ceramic structure is a fully dense monolith, i.e. 99% or greater theoretical density.
  • the present invention also provides a method of making a ceramic structure, the method comprising
  • the ceramic structure contains from about 0.01 wt% to about 20 wt% sulfur, such as from about 0.1 wt% to about 10 wt% sulfur.
  • the produced ceramic structure may be characterized by at least 50% theoretical density, preferably at least 75% theoretical density, and more preferably at least 95% theoretical density.
  • the ceramic structure is a fully dense monolith.
  • compositions also referred to as formulations
  • structures, systems, and methods of the present invention will be described in detail by reference to various non-limiting embodiments.
  • Variations of this invention provide resin formulations which may be used for 3D printing (e.g., by stereolithography) of an intermediate structure followed by thermally treating (e.g., by firing or pyrolyzing) to convert the 3D intermediate structure part into a 3D ceramic structure.
  • the ceramic materials may be prepared from one or more disclosed preceramic resin formulations that can be used in UV-cure-based 3D printing (stereolithography), for example, to form polymer parts which enable direct thermal conversion to ceramics.
  • Preceramic in this disclosure simply refers to the capability to be ultimately converted to a ceramic material. It is noted that the disclosed preceramic resin formulations are precursors to preceramic polymers, which themselves are precursors to ceramic materials.
  • Variations of the invention enable direct, free-form 3D printing of preceramic polymers which can be converted to dense ceramics, or even fully dense ceramics.
  • the preceramic resin formulations are preferably compatible with stereolithography photopolymerization.
  • the monomers and polymeric systems can be printed into potentially complex 3D shapes.
  • Preferred preceramic resin formulations allow the ceramic structures to be formed with high thermal stability and mechanical strength.
  • the disclosed resin formulations can be economically converted into structures that are lightweight, strong, and stiff-but can withstand a high-temperature oxidizing environment.
  • Final interconnected three-dimensional ceramic materials include, but are not limited to, silicon oxycarbide (SiOC), silicon carbide (SiC), silicon nitride (Si 3 N 4 ), silicon oxynitride (SiON), silicon carbonitride (SiCN), silicon boronitride (SiBN), silicon boron carbonitride (SiBCN), and boron nitride (BN).
  • SiOC silicon oxycarbide
  • SiC silicon carbide
  • Si 3 N 4 silicon nitride
  • SiON silicon carbonitride
  • SiCN silicon boronitride
  • SiBCN silicon boron carbonitride
  • BN boron nitride
  • the 3D ceramic material is prepared directly from 3D printed preceramic polymer material, which is prepared from preceramic resin formulations.
  • the 3D printing may be accomplished though UV-cure methods via stereolithography with laser rastering, DLP (digital light processing), and/or LCDP (liquid crystal device projector) projection, for example.
  • preceramic resin formulation comprising:
  • a "resin” means a composition capable of being polymerized or cured, further polymerized or cured, or crosslinked. Resins may include monomers, oligomers, prepolymers, or mixtures thereof.
  • the first molecule is present from about 3 wt% to about 97 wt% of the formulation, such as about 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt%, for example.
  • the non-carbon atom may be present in the main chain, in side chains, or in both of these.
  • the first molecule may include one or more functional groups selected from the group consisting of vinyl, ethynyl, vinyl ether, vinyl ester, vinyl amide, vinyl triazine, vinyl isocyanurate, acrylate, methacrylate, diene, triene, and functional analogs thereof. In some embodiments, the first molecule includes two or more of such functional groups.
  • a “functional analog” herein means that the functional group has similar chemical and reactive properties, with respect to the polymerization of the preceramic resin formulation.
  • the second molecule is included in the preceramic resin formulation, the second molecule is present from about 0.1 wt% to about 97 wt% of the formulation, such as about 0.2, 0.5, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt%, for example.
  • the second molecule may include one or more functional groups selected from the group consisting of thiol, alkyl, ester, amine, hydroxyl, and functional analogs thereof.
  • the second molecule may be chemically contained within one or more functional groups selected from the group consisting of thiol, alkyl, ester, amine, hydroxyl, and functional analogs thereof.
  • the R group may be, or include, an inorganic group containing an element selected from the group consisting of Si, B, Al, Ti, Zn, P, Ge, S, N, O, and combinations thereof.
  • At least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% (mole percent) of the R group is inorganic, i.e. not carbon. In certain embodiments, at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% (mole percent) of the R group is specifically Si.
  • the R group may be present in the main chain, in side chains, or in both of these.
  • the non-carbon atom of the R group, when it is inorganic, may be the same as or different than the non-carbon atom in the first molecule.
  • the weight ratio of second molecule to first molecule may vary from about 0 to about 32, such as about 0.5, 1, 2, 3, 5, 10, 15, 20, 25, or 30. In some embodiments, the weight ratio of second molecule to first molecule is dependent on the ratio of thiol to vinyl. For example, in certain embodiments there is at least one thiol functional group available per vinyl group.
  • the photoinitiator may be present from about 0.001 wt% to about 15 wt% of the formulation, for example.
  • the photoinitiator may be present at about 0.002, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% of the formulation, for example.
  • the thermal free-radical initiator may be present at about 0.002, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% of the formulation, for example.
  • both a photoinitiator and thermal free-radical initiator may each be present at about 0.001, 0.002, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, or 5 wt% of the formulation, for example.
  • the photoinitiator and/or the thermal free-radical initiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, camphorquinone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, benzophenone, benzoyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, camphorquinone, oxygen, nitrogen dioxide, and combinations or derivatives thereof.
  • Other photoinitiators or thermal free-radical initiators may be utilized.
  • a thermal free-radical initiator may be useful, for example, to crosslink unreacted vinyl groups remaining which have not reacted with the thiol group.
  • a thermal free-radical initiator may also be useful to react vinyl group(s) with other available functional groups such as, but not limited to, methyl or hydro groups in the first or second molecule, thereby creating a second type of reaction mechanism.
  • the formulation further includes a radiation-trigger free-radical initiator that is active at a wavelength substantially different from the photoinitiator.
  • the preceramic resin formulation includes a thermal free-radical initiator
  • the formulation further includes a radiation-trigger free-radical initiator.
  • the free-radical inhibitor may be present from about 0.001 wt% to about 10 wt% of the formulation, for example. In various embodiments, the free-radical inhibitor may be present at about 0.002, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% of the formulation, for example.
  • the free-radical inhibitor may be selected from the group consisting of hydroquinone, methylhydroquinone, ethylhydroquinone, methoxyhydroquinone, ethoxyhydroquinone, monomethylether hydroquinone, propylhydroquinone, propoxyhydroquinone, tert-butylhydroquinone, n-butylhydroquinone, and combinations or derivatives thereof.
  • a "3D-printing resolution agent” is a compound that improves print quality and resolution by containing the curing to a desired region of the laser or light exposure.
  • the 3D-printing resolution agent may be present from about 0.001 wt% to about 10 wt% of the formulation, for example.
  • the 3D-printing resolution agent may be present at about 0.002, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% of the formulation, for example.
  • the 3D-printing resolution agent may be selected from UV absorbers, fluorescent molecules, optical brighteners, or combinations thereof.
  • the 3D-printing resolution agent is selected from the group consisting of 2-(2-hydroxyphenyl)-benzotriazole, 2-hydroxyphenyl-benzophenones, 2-hydroxyphenyl-s-triazines, 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole), 2,2'-(1,2-ethenediyl)bis(4,1-phenylene)bisbenzoxazole, and combinations or derivatives thereof.
  • a preceramic resin formulation comprising the following components.
  • the first molecule also contains at least one non-carbon atom in the main chain or in side chains.
  • non-carbon atoms that can be used include, but are not limited to, Si, B, Al, Ti, Zn, O, N, P, S, or Ge.
  • X when X is O, the non-carbon atom is not O; or when X is N, the non-carbon atom is not N.
  • the non-carbon atoms can be a part of cyclic or acyclic groups or structures.
  • first component molecules include, but are not limited to, trivinylborazine; 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane; 1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane; 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane; 2,2,4,4,6,6-hexakisallyloxyl-triazatriphosphinine; tetraallyloxysilane; vinyl-terminated polydimethylsiloxane; tetravinylsilane; vinyl-terminated polydimethylsiloxane-ethylene copolymer; divinyldimethylsilane; 1,2-divinyltetramethyldisilane; 1,4-bis(vinyldimethylsilyl)benzene
  • the first molecule may be between 3% to about 97% by weight of the resin formulation.
  • the molecules R-Y-H can contain two or more YH groups in the structure that can be used in the polymerization.
  • the second molecule comprises two or more SH groups, i.e. thiol or mercapto groups.
  • the R groups can be organic groups such as alkyl groups, esters, amines, or hydroxyl, or inorganic non-carbon-containing atoms or groups, which may be part of cyclic or acyclic structures.
  • inorganic non-carbon atoms or groups in the main chain or side chains include, but are not limited to, Si, B, Al, Ti, Zn, P, Ge, S, O, N, or combinations thereof.
  • the R group when Y is O, the R group is not O; or when Y is N, the R group is not N.
  • Examples of the second component includes, but not limited to, pentaerythritol tetrakis(3-mercaptopropionate); trimethylolpropanetris(2-mercaptoacetate); trimethylolpropane tris(3-mercaptopropionate); tetrakis(dimethyl-3-mercaptopropylsiloxy)silane; tetrakis(dimethyl-2-mercaptoacetate siloxy)silane; (mercaptopropyl)methylsiloxane]-dimethylsiloxane copolymer; mercaptopropyl)methylsiloxane homopolymer; and pentaerythritol tetrakis(2-mercaptoacetate).
  • the second molecule is generally between 0% and about 97% by weight of the resin formulation.
  • the ratio of second molecule to first molecule may vary widely, from 0 to 10, 20, 30 or more. This ratio will influence the polymerization reaction rate as well as the polymer composition.
  • a photoinitiator generates free radicals under light exposure from light having a wavelength from about 200 nm to about 500 nm, for example.
  • the photoinitiator is more than 0% to about 10% or less total weight of the resin formulation.
  • One or a combination of different types of photoinitiators can be used in the polymerization process and usually result in different reaction rates. Examples of photoinitiators include, but are not limited to, 2,2-dimethoxy-2-phenylacetophenone; 2-hydroxy-2-methylpropiophenone; camphorquinone; bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide; benzophenone; and benzoyl peroxide.
  • a free-radical thermal initiator is included, which generates free radicals under elevated temperature conditions.
  • the free-radical thermal initiator is present up to about 10% or less total weight of the resin formulation.
  • thermal initiators include, but are not limited to, benzoyl peroxide, dicumyl peroxide, and 2,2'-azobisisobutyronitrile.
  • a free-radical inhibitor is added in a sufficient amount to the resin formulation to inhibit unwanted polymerization of regions outside the desired printing area so as to allow sufficient resolution to the desired part.
  • the free-radical inhibitor inhibits unwanted polymerization of regions outside an optical waveguide so as to allow formation of preceramic-polymer waveguides.
  • free-radical inhibitors include, but are not limited to, hydroquinone; methylhydroquinone; ethylhydroquinone; methoxyhydroquinone; ethoxyhydroquinone; monomethylether hydroquinone; propylhydroquinone; propoxyhydroquinone; tert-butylhydroquinone; and n-butylhydroquinone.
  • the free-radical inhibitor is typically selected to be from about 0.001% to about 1% by weight of the total resin formulation.
  • UV absorbers, fluorescents, or optical brighteners are preferably included to absorb light at the desired wavelength and convert the energy either into thermal energy or radiation at a higher wavelength.
  • UV absorbers, fluorescents, or optical brighteners are preferably included to absorb light at the desired wavelength and convert the energy either into thermal energy or radiation at a higher wavelength.
  • UV absorbers include, but are not limited to, 2-(2-hydroxyphenyl)-benzotriazole , 2-hydroxyphenyl-benzophenones, 2-hydroxyphenyl-s-triazines, 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole), and 2,2'-(1,2-ethenediyl)bis(4,1-phenylene)bisbenzoxazole.
  • a ceramic structure produced by polymerization, 3D printing, and thermal treatment (e.g., pyrolysis or sintering) of a preceramic resin formulation comprising:
  • the ceramic structure contains from about 0.01 wt% to about 20 wt% sulfur, such as from about 0.1 wt% to about 10 wt% sulfur. In various embodiments, the ceramic structure contains about 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt% sulfur.
  • the ceramic structure may be characterized by at least 50% theoretical density, preferably at least 75% theoretical density, and more preferably at least 95% theoretical density.
  • theoretical density it is meant the actual density of the ceramic structure as a percentage of theoretical density of the material itself, calculated in the absence of porous voids.
  • the ceramic structure is characterized by a theoretical density of about (or at least about) 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5%.
  • the ceramic structure is a fully dense monolith, which means that the ceramic structure has at least 99% (e.g., essentially 100%) theoretical density associated with a part or continuous region of material (a "monolith").
  • the absolute density in g/cm 3 will vary, depending on the selection of base materials; an exemplary range is about 1 g/cm 3 to 3 g/cm 3 .
  • the present invention also provides a method of making a ceramic structure, the method comprising
  • the ceramic structure contains from about 0.01 wt% to about 20 wt% sulfur, such as from about 0.1 wt% to about 10 wt% sulfur. In various methods, the final ceramic structure contains about 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt% sulfur.
  • the produced ceramic structure may be characterized by at least 50% theoretical density, preferably at least 75% theoretical density, and more preferably at least 95% theoretical density.
  • the ceramic structure is characterized by a theoretical density of about (or at least about) 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5%.
  • the ceramic structure is a fully dense monolith.
  • a method of making a ceramic structure may include first polymerizing a preceramic resin formulation, followed by 3D printing of the already-made polymer.
  • the polymerizing and 3D printing steps are performed simultaneously, at a desired location (e.g., a layer) within a part.
  • the polymerizing and 3D printing steps are performed semi-simultaneously, in which multiple steps are performed overall while at each step, some amount of polymerizing and some amount of 3D printing takes place.
  • the curing or conversion of preceramic resin formulation to preceramic polymer includes crosslinking.
  • a crosslink is a bond that links one polymer chain to another.
  • Crosslink bonds can be covalent bonds or ionic bonds. When polymer chains are linked together by crosslinks, they lose some of their ability to move as individual polymer chains.
  • Crosslinks are the characteristic property of thermosetting plastic materials. In most cases, crosslinking is irreversible.
  • a gel is formed first, followed by a solid material as the monomer conversion is further increased to crosslink chains together.
  • a "gel” is a solid, jelly-like material that can have properties ranging from soft and weak to hard and tough. Gels exhibit no flow when in the steady-state. By weight, gels are mostly liquid, yet they behave like solids due to a three-dimensional crosslinked network within the liquid.
  • Some variations of the invention utilize a self-propagating polymer waveguide, as described in commonly owned U.S. Patent No. 7,687,132 issued March 30, 2010 to Gross et al. ; U.S. Patent No. 9,341,775 issued May 17, 2016 to Eckel et al. ; U.S. Patent No. 9,377,567 issued June 28, 2016 to Jacobsen et al. ; and U.S. Patent No. 9,528,776 issued December 27, 2016 to Roper et al. , which are hereby incorporated by reference herein. Without being limited by speculation or theory, it is hypothesized that initial exposure of monomer to a collimated beam can initiate microgel sites within the liquid monomer layer.
  • microgel sites have a higher crosslink density than the surrounding monomer/polymer, which leads to a higher localized refractive index.
  • the higher refractive index at the microgel site may act as a lens.
  • the focused energy from the incident beam leads to initial "waveguide" formation in the direction of the incident (primary) beam, where the refractive index of the waveguide is higher than the surrounding monomer/polymer.
  • U.S. Patent No. 7,382,959 issued June 3, 2008 to Jacobsen is hereby incorporated by reference herein for its description of mechanisms involving self-propagating polymer waveguide formation.
  • sufficient polymerization inhibitor and UV absorber are added to the resin formulation to confine the polymerization to the laser exposure point and to minimize scatter to maintain fidelity in the features of the printed part. UV light is then scanned across the resin surface to expose a cross section and build up a thin slice of the part to be manufactured. Although in principle any geometry can be fabricated with this approach, the process is slow, because every thin layer has to be exposed separately.
  • Structures with linear features extending from the exposure surface can be formed much more rapidly when utilizing the self-propagating photopolymer waveguide technology.
  • Monomers are selected to promote a change in the index of refraction upon polymerization, which causes internal reflection of the UV light, trapping it in the already-formed polymer. This exploits a self-focusing effect that forms a polymer waveguide, tunneling the light toward the tip of the waveguide and causing it to polymerize further. This reduces the need for additives that control scatter and UV absorption.
  • the architecture of the material or structure can then be defined by a patterned mask that defines the areas exposed to a collimated UV light source, for example.
  • the polymer crosslink density depends on exposure parameters and can be increased by thermal treatments or additional UV exposure. Unpolymerized resin may be recycled and reused.
  • the photoinitiator generates free radicals under light exposure by one of intramolecular bond cleavage or intermolecular hydrogen abstraction.
  • the monomer will polymerize when exposed to UV light (wavelengths of 10 nm to 400 nm), although photoinitiators may be used to initiate polymerization when exposed to other wavelengths, such as in the visible spectrum.
  • light exposure is produced from light having one or more wavelengths selected from about 200 nm to about 700 nm, such as about 250, 300, 350, 400, 500, or 600 nm.
  • a thermal post-cure of the 3D polymer is performed, after the 3D printing but prior to the pyrolysis to produce the ceramic structure.
  • the 3D polymer may be heated to a temperature of about 60°C to about 500°C, such as about 250°C to about 400°C, for a thermal post-cure time of about 10 minutes to about 8 hours, such as about 20 minutes to about 2 hours.
  • a thermal initiator is present.
  • a thermal treatment is then conducted.
  • the direct conversion of a preceramic 3D-printed structure to a ceramic structure may be achieved by pyrolysis, sintering, annealing, calcination, or another thermal treatment technique.
  • the thermal treatment is preferably performed following polymerization and any (optional) thermal post-cure of the 3D polymer.
  • the thermal treatment is combined (i.e., overlaps in time and/or temperature) with polymerization, thermal post-cure, or both. It will also be recognized that even when a sequential operation is intended, some amount of ceramic formation may occur prior to a planned step of thermal treatment, as a result of the intrinsic kinetics and thermodynamics of the reaction system.
  • the thermal treatment is based on heating the 3D-printed structure for an extended period of time (such as from 10 minutes to 1 week) under various inert or reactive atmospheres, such as N 2 , Ar, air, CH 4 , C 2 H 6 , C 2 H 4 , CO, CO 2 , or a combination of these gases.
  • the thermal treatment may include heating at a rate of 0.1°C/min to 20°C/min from ambient temperature (e.g. about 25°C) to 1000°C, dwelling at 1000°C for at least 15 minutes, and then cooling at a rate of -0.1°C/min to -20°C/min back to ambient temperature.
  • the dwell temperature may vary; for example, dwell temperatures of about 500°C to about 1500°C may be employed.
  • a reactive thermal treatment is performed, in which the gas is reactive toward the initial polymer, the final ceramic material, or both of these.
  • the gas When the gas is reactive, it may react with a component and cause it to leave the material. Alternatively, or additionally, the gas may react with a component and remain with the base material. It is also possible for the gas to react and form products, some of which depart from the material while the rest remains with the material.
  • Reactive gases may be selected from O 2 , O 3 , air, CO, CO 2 , H 2 , H 2 O, CH 4 , SO 2 , H 2 S, NH 3 , NO, NO 2 , and N 2 O, and so on.
  • the maximum temperature for reactive thermal treatment may be, for example, about 300°C to about 1500°C.
  • the system pressure may also be adjusted to influence the gas atmosphere.
  • liquid or solid additives may be introduced into the preceramic resin formulation, the preceramic polymer, or both of these, to enhance the conversion to a ceramic structure.
  • additives to seed crystallization or phase formation may be introduced.
  • the additives may include nanoparticles, such as nanoparticle metal oxides, for example.
  • the escaping gases or vapors may include (but are by no means limited to) CH 4 , H 2 , CO, CO 2 , H 2 O, SO 2 , etc.
  • the overall mass loss associated with the conversion of preceramic polymer to the ceramic structure may vary widely, such as from about 1 wt% to about 90 wt%, e.g. about 5, 10, 20, 30, 40, 50, 60, 70, or 80 wt%.
  • the overall mass loss will be dictated by the starting formulation (e.g., fraction organic versus inorganic) as well as by process parameters. In principle, the lost mass may be recovered separately and used for other purposes.
  • Associated with mass loss may be shrinkage of the preceramic polymer as it converts to the ceramic structure.
  • the linear shrinkage (calculated in a single dimension, such as height of part) may be from 0% to about 60%, for example. Note that the mass loss and shrinkage are not necessarily correlated. In some embodiments with high mass loss, there is not much (if any) shrinkage. These embodiments tend to produce higher porosity and therefore lower densities. In some embodiments with high mass loss, there is substantial shrinkage. These embodiments tend to produce lower porosity, or no porosity, and therefore higher densities (e.g., fully dense ceramic materials). Finally, in some embodiments, there is little mass loss but shrinkage associated with chemical reactions taking place. These embodiments also tend to produce relatively high densities.
  • the bulk shape (relative geometry) of the preceramic 3D-printed polymer may be preserved in the final ceramic structure. That is, when shrinkage is uniform in all dimensions, the geometrical features are retained in the part: it is a scaled-down version, in all three dimensions.
  • shrinkage is approximately uniform, which means the geometrical features are basically maintained, with slight deviations. Uniform shrinkage is possible when there is no random fragmentation during conversion of the preceramic polymer to the ceramic structure, and when the reactions and gas escape are isotropic within the material. Note that very small features, such as at the nanoscale, may not be preserved during otherwise uniform shrinkage.
  • net shape means that the geometrical features are retained, so that manufactured parts allow final fabrication matching the intended design with little or no post-processing.
  • Near net shape means that the geometrical features are not perfectly retained but require only minimal post-processing or hand-work. Both net-shape parts and near-net-shape parts require little or no machining, polishing, bonding, surface finishing, or assembly.
  • the configuration and microstructure of the preceramic polymer determine the composition, microstructure, and yield of the ceramic material after thermal treatment.
  • a high crosslink density is preferred to prevent the fragmentation and loss of low-molecular-mass species, which have not fully converted to either ceramic or escaping gases, during thermal treatment.
  • the thermal treatment may produce ceramic structures which include, but are certainly not limited to, SiC, SiOC, Si 3 N 4 , SiON, SiCN, SiBN, SiBCN, or BN.
  • the fraction of carbon may be tailored, for example, by adding phenyl groups on the side chain of the polymer or by using a carbon-based crosslinking agent such as divinyl benzene.
  • the density of the final ceramic part may vary, as explained above. In general (without limitation), absolute densities ranging from about 0.1 g/cm 3 to about 5 g/cm 3 , such as about 1-3 g/cm 3 , may be produced. A fully dense ceramic may have a density from about 1 g/cm 3 to about 4 g/cm 3 , for example.
  • the strength of the final ceramic material will vary, depending on the initial preceramic resin formulation, as well as the processing parameters.
  • the engineering strength of a ceramic part also will depend on the geometry-such as a microtruss produced by some embodiments employing a self-propagating polymer waveguide technique. It is noted that, for instance, silicon oxycarbide microlattice and honeycomb cellular materials fabricated with the present methods exhibit higher strength than ceramic foams of similar density.
  • the thermal stability of the final ceramic material will vary, depending primarily on the initial preceramic resin formulation, as well as the processing parameters.
  • the ceramic structure is characterized by being stable in the presence of air at a temperature of about 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, 1600°C, 1700°C, or 1800°C.
  • the final ceramic structure even when no machining, polishing, bonding, surface finishing, or assembly is required, may be subjected to coloring (e.g., with inks or dyes), stamping, or other non-functional features, if desired.
  • coloring e.g., with inks or dyes
  • stamping e.g., stamping, or other non-functional features
  • Example 1 Preceramic Stereolithography-Printed Polymer for Fabrication of 3D Ceramic Structure.
  • the material mixture is then readily used for the stereolithography.
  • the 3D print is performed using a Formlabs 1, SLA (Formlabs, Somerville, MA, U.S.) with laser wavelength at 405 nm.
  • the step size is 100 microns, and the resin setting is "Flexible.”
  • the preceramic resin formulation is printed into a preceramic polymer part.
  • FIG. 1 shows a top-view photograph of the preceramic polymer part
  • FIG. 2 shows a side-view photograph of the preceramic polymer part.
  • FIG. 3 shows a side-view photograph of the ceramic part resulting from the pyrolysis. Approximately uniform shrinkage is observed ( FIG. 3 compared to FIG. 2 ). The steps from the layer-by-layer print can be seen in all three pictures ( FIGS. 1 , 2 , and 3 ).
  • the direct, near-net-shaped conversion of a preceramic 3D-printed polymer structure to a ceramic structure is achieved by pyrolysis to produce the ceramic 3D structure shown in FIG. 3 .

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